US3205194A - Imidazolidine thione hydrochloric acid salts as stabilizers - Google Patents
Imidazolidine thione hydrochloric acid salts as stabilizers Download PDFInfo
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- US3205194A US3205194A US163896A US16389662A US3205194A US 3205194 A US3205194 A US 3205194A US 163896 A US163896 A US 163896A US 16389662 A US16389662 A US 16389662A US 3205194 A US3205194 A US 3205194A
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- thione
- hydrochloric acid
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- diazadispiro
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
- C08K5/3447—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
Definitions
- This invention relates to the use of imidazolidine thione hydrochloric acid salts as stabilizers for polymers and their vulcanizates. It includes the stabilizer polymers and vulcanizates as well as their preparation.
- the polymers and their vulcanizates are prepared in any usual manner, and the stabilizer is added at a convenient stage, preferably just prior to coagulation of the polymer or polymers.
- hydrochloric acid salts have substantially the same solubility in water as that of the parent compound 7,14-diazadispiro- [5. 1.5.2] -pentadecane-l5-thione. They are less soluble than the sulfuric acid and nitric acid salts which have about the same solubility. These latter are less soluble than the phosphoric acid salt.
- This solubility order may explain the relative activities of these materials in polymers and rubbers.
- the solubility of any of these salts can be altered by adding solutes to the water, and non-aqueous solvents may be utilized for this purpose.
- the stabilizers of this invention include more particularly the hydrochloric acid salts of compounds of which the following are illustrative:
- the following example illustrates the preparation of the use of the hydrochloric acid salts.
- the high concentrations in water required to add the more water-soluble salts to the polymer in latex form make their use commercially impractical because of the expense.
- the example illustrates the use of the salts as stabilizers in SBR, styrene-butadiene polymer rubber. They can likewise be used in the stabilization of other emulsion polymers of diene elastorners.
- the salts are non-staining and polymers containing them age with substantially no discoloration.
- the following example illustrates the preparation of the hydrochloric acid salt which is useful as stabilizer.
- the parent compound, 7,14-diazadispiro-[5.1.5.21-pentadecane-lS-thione has the following formula:
- Stabilizer B The parent compound 7,l4-diazadispiro- [5.1.5.2]-pentadecane-15-thione.
- Stabilizer I per 100 parts of SBR were employed, and for the imidazolidine thione stabilizers only 0.5 part per 100 parts of SBR. The stabilizers were added to the SBR latexes prior to coagulation.
- Table II shows the normal and aged physical properties of vulcanizates obtained from SBR polymer containing j Oil 'Stearie Acid. Zinc Oxide" Normal Stress-Strain:
- Stabilizers A, B, and I were cured for 30 minutes at 300 F.
- TAB LE II Total 300% Modulus, p.s.i Tensile, p.s.i. Elongation, percent" Aged 2 days at 212F.Ov
- the examples are illustrative.
- the amount of stabilizer used will in general be between 0.1 and parts per hundred parts of the polymer or vulcanizate, by weight.
- the method of stabilizing elastomer emulsion polymer composed of a substantial portion of hydrocarbon diene polymer which comprises adding to an emulsion of the polymer before coagulation a stabilizing amount of the hydrochloric acid salts of imidazolidine thiones of the formula and lower alkyl derivatives thereof substituted on methylene groups which are connected to two other methylene groups,thereafter coagulating the emulsion and thereby incorporating stabilizer in the polymer, and then subjecting the resulting polymer composition to heat aging.
- the method of stabilizing the vulcanizate of an elastomer emulsion polymer composed of a substantial portion of hydrocarbon diene polymer which comprises vulcanizing the same in the presence of a stabilizing amount of the hydrochloric acid salt of an imidazolidine thione of the formula I CH 7 and lower alkyl derivatives thereof substituted on methm rim H3O CH2 5 l Hg CH3 and lower alkyl derivatives thereof substituted on methylene groups which are connected to two other methylene groups.
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
United States Patent 3,205,154 MIDAZOLIDINE THION'E HYDROCHLORIC ACID SALTS AS STABILIZERS Arthur E. Oberster, North Canton, and Wendell S. Cook, Canal Fulton, Ohio, assignors to The Firestone Tire & Rubber Company, Akron, Ohio, a corporation of Ohio No Drawing. Filed Jan. 2, 1962, Ser. No. 163,896
11 Claims. (Cl. 260-453) This invention relates to the use of imidazolidine thione hydrochloric acid salts as stabilizers for polymers and their vulcanizates. It includes the stabilizer polymers and vulcanizates as well as their preparation.
Various derivatives of imidazolidine-4-thiones are known in the literature.
Salts of 7,14-diazadispiro-[5.1.5.2]-pentadecane-15- thione and lower alkyl derivatives thereof substituted on methylene groups which are connected to two other methylene groups, and particularly the hydrochloric acid salts re stabilizers of diene elastomer emulsion polymers comosed of a substantial portion of hydrocarbon diene polymer (for example, butadiene rubbers, styrene-butadiene rubbers, nitrile-butadiene rubbers, acrylate-butadiene rubbers, isoprene rubbers (synthetic)) and their vulcanizates. The polymers and their vulcanizates are prepared in any usual manner, and the stabilizer is added at a convenient stage, preferably just prior to coagulation of the polymer or polymers.
The solubility of the salts in water varies over a considerable range. The relative solubility order of these salts is as follows:
The least soluble are given first, and the most soluble last. The hydrochloric acid salts have substantially the same solubility in water as that of the parent compound 7,14-diazadispiro- [5. 1.5.2] -pentadecane-l5-thione. They are less soluble than the sulfuric acid and nitric acid salts which have about the same solubility. These latter are less soluble than the phosphoric acid salt.
This solubility order may explain the relative activities of these materials in polymers and rubbers. The solubility of any of these salts can be altered by adding solutes to the water, and non-aqueous solvents may be utilized for this purpose.
The stabilizers of this invention include more particularly the hydrochloric acid salts of compounds of which the following are illustrative:
3, 1 1-dimethyl-7, l4-diazadispiro- [5.1 .5.2]
pentadecane- IS-thione 3,1l-di-t-butyl-7,14-diazadispiro-[5.1.5.2]-
pentadecane- 15 -thione 3, 1 1-di-t-amyl-7, l4-diazadispiro- [5 1.5.2]
pentadecane- 15-thione 3,1 l-di-n-butyl-7, l4-diazadispiro- [5. 1.5.2]
pentadecane-l S-thione 2,10-dimethyl-7,l4-diazadispiro-[5.1.5.2]-
pentadecanel5-thione 2,10-di-n-butyl-7,14-diazadispiro-[5.1.5.2]-
pentadecane-lS-thione 2,10-di-tt-octyl-7,14-diazadispiro-[5.1.5.2]-
pentadecane-15-thione 3,1l-dicyclohexyl-7,14-diazadispiro-[5.1.5.2]-
pentadecane- 1 S-thione 3,1l-diisopropylfl,l4-diazadispiro-[5.1.5.2]-
pentadecane- 15 -thione 2,10-diethyl-7, l4-diazadispiro- [5 1.5.2]
pentadecane-lS-thione 2,4,10,12-tetramethyl-7,14-diazadispiro-[5.1.5.2]-
pentadecane- 15-thione 2,3,10,1l-tetraethyl-7,14-diazadispiro-[5.1.5.2]-
pentadecane-l 5-thione 3,205,194 Patented Sept. 7, 1965 The following example illustrates the preparation of the use of the hydrochloric acid salts. The high concentrations in water required to add the more water-soluble salts to the polymer in latex form make their use commercially impractical because of the expense. The example illustrates the use of the salts as stabilizers in SBR, styrene-butadiene polymer rubber. They can likewise be used in the stabilization of other emulsion polymers of diene elastorners. The salts are non-staining and polymers containing them age with substantially no discoloration.
The following example illustrates the preparation of the hydrochloric acid salt which is useful as stabilizer. The parent compound, 7,14-diazadispiro-[5.1.5.21-pentadecane-lS-thione has the following formula:
HgC (4) (2) CH2 Hz (5) 1) H2 \(6)/ Hz (10) (12) Hz 11 The example follows:
EXAMPLE Hydrochloric acid salt of 7,14-diazadispiro-[5J.5.2]-
pentadecane-15-thi0ne The parent compound (60 grams) was suspended in a mixture of ml. of concentrated hydrochloric acid and 300 ml. of water. This suspension was stirred vigorously for two hours. The reaction mixture was filtered, the product was washed with cold water and allowed to dry on the filter. This resulted in 67 grams of product melting at 275 C. (d.)
In the following tables comparison has been made with a widely used commercial stabilizer for SBR polymer which is identified as Stabilizer I, and this and a stabilizer of this invention were tested and compared with the parent compound, these latter stabilizers being identified in the following tables as:
Stabilizer Azhydrochloric acid salt of 7,14-diazadispiro- [5.1.5.2]-pentadecane-15-thione.
Stabilizer B::The parent compound 7,l4-diazadispiro- [5.1.5.2]-pentadecane-15-thione.
In the tests 1.25 parts of Stabilizer I per 100 parts of SBR were employed, and for the imidazolidine thione stabilizers only 0.5 part per 100 parts of SBR. The stabilizers were added to the SBR latexes prior to coagulation.
In Table I, the effects of oven aging SBR polymer containing stabilizers of this invention and the commercial stabilizer are compared before and after aging four days in an air circulating oven at 70 C.
Table II shows the normal and aged physical properties of vulcanizates obtained from SBR polymer containing j Oil 'Stearie Acid. Zinc Oxide" Normal Stress-Strain:
Stabilizers A, B, and I, respectively, in the different amounts previously described when compounded as indicated in the heading of the table. The various stocks were cured for 30 minutes at 300 F.
TAB LE II Total 300% Modulus, p.s.i Tensile, p.s.i. Elongation, percent" Aged 2 days at 212F.Ov
200% Modulus, p.s.i Tensile, p.s.i Elongation, percent Aged 5 Hours at 260 F 200% Modulus, p.s. Tensile, p.s.i Elongation, percent The results show that the stabilizer of this invention, the parent compound from which it was formed, and the commercial stabilizer all are effective in stabilizing the vulcanizate.
It is to be noted that in the various tests the amount of the commercial stabilizer was 2.5 times that of the stabilizer of this invention.
The examples are illustrative. The amount of stabilizer used will in general be between 0.1 and parts per hundred parts of the polymer or vulcanizate, by weight.
What weclaim is:
1. The method of stabilizing elastomer emulsion polymer composed of a substantial portion of hydrocarbon diene polymer which comprises adding to an emulsion of the polymer before coagulation a stabilizing amount of the hydrochloric acid salts of imidazolidine thiones of the formula and lower alkyl derivatives thereof substituted on methylene groups which are connected to two other methylene groups,thereafter coagulating the emulsion and thereby incorporating stabilizer in the polymer, and then subjecting the resulting polymer composition to heat aging.
2. The method of claim 1 in which the polymer is styrene-butadiene rubber polymer.
3. v The method of claim 1 in which the polymer is styrene-buta-diene rubber polymer and the stabilizer is the hydrochloric acid salt of unsubstituted imidazolidine thione.
4. The method of stabilizing the vulcanizate of an elastomer emulsion polymer composed of a substantial portion of hydrocarbon diene polymer which comprises vulcanizing the same in the presence of a stabilizing amount of the hydrochloric acid salt of an imidazolidine thione of the formula I CH 7 and lower alkyl derivatives thereof substituted on methm rim H3O CH2 5 l Hg CH3 and lower alkyl derivatives thereof substituted on methylene groups which are connected to two other methylene groups.
8. The product of claim 7 in which the product is a polymer.
9. The product of claim 8 in which the polymer is styrene-butadiene rubber polymer.
10. The product of claim 7 in which the product is a vulcanizate.
11. The product of claim 7 in which the stabilizer is hydrochloric acid salt of unsubstituted imidazolidine thione.
References Cited by the Examiner UNITED STATES PATENTS 2,785,175 3/57 Christian 260-309.7
2,806,036 9/57 Christian 260-309] 2,842,553 7/58 Christian 2603 09.7
LEON I. BERCOVITZ, Primary Examiner.
JOSEPH R. LIBERMAN, Examiner.
Claims (1)
1. THE METHOF OF STABILIZING ELASTOMER EMULSION POLYMER COMPOSED OF A SUBSTANTIAL PORTION OF HDROCARBON DIENE POLYMER WHICH COMPRISES ADDING TO AN EMULSION OF THE POLYMER BEFORE COMAGULATION A STABILIZING AMOUNT OF TE HYDROCHLORIC ACID SALTS OF IMIDAZOLIDINE THIONES OF THE FORMULA
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US163896A US3205194A (en) | 1962-01-02 | 1962-01-02 | Imidazolidine thione hydrochloric acid salts as stabilizers |
| US388943A US3275650A (en) | 1962-01-02 | 1964-08-11 | 7-nitroso-7, 14-diazadispiro-[5.1.5.2]-pentadecane-15-thione and lower alkyl detrivatives thereof |
| US462722A US3311588A (en) | 1962-01-02 | 1965-06-09 | 7-nitroso imidazolidine thiones as stabilizers for diene elastomers and their vulcanizates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US163896A US3205194A (en) | 1962-01-02 | 1962-01-02 | Imidazolidine thione hydrochloric acid salts as stabilizers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3205194A true US3205194A (en) | 1965-09-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US163896A Expired - Lifetime US3205194A (en) | 1962-01-02 | 1962-01-02 | Imidazolidine thione hydrochloric acid salts as stabilizers |
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| Country | Link |
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| US (1) | US3205194A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330800A (en) * | 1964-02-13 | 1967-07-11 | Firestone Tire & Rubber Co | Process for coagulating butadiene polymers in the presence of an imidazolidine-15-thione stabilizer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2785175A (en) * | 1955-12-15 | 1957-03-12 | Monsanto Chemicals | Imidazolidinethiones |
| US2806036A (en) * | 1957-09-10 | Process for preparation of | ||
| US2842553A (en) * | 1955-07-13 | 1958-07-08 | Monsanto Chemicals | Process of preparing imidazolidinethiones |
-
1962
- 1962-01-02 US US163896A patent/US3205194A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2806036A (en) * | 1957-09-10 | Process for preparation of | ||
| US2842553A (en) * | 1955-07-13 | 1958-07-08 | Monsanto Chemicals | Process of preparing imidazolidinethiones |
| US2785175A (en) * | 1955-12-15 | 1957-03-12 | Monsanto Chemicals | Imidazolidinethiones |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330800A (en) * | 1964-02-13 | 1967-07-11 | Firestone Tire & Rubber Co | Process for coagulating butadiene polymers in the presence of an imidazolidine-15-thione stabilizer |
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